phd presentation 3rd feb 2016
TRANSCRIPT
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ADVANCEMENT OF ADSORPTION PROCESS ON ACTIVATED CARBON USING MICROWAVE AND HIGH GRAVIMETRIC TECHNOLOGIES
Presented By
Anirban Kundu (SHC 110090)Institute of Biological Science, University of Malaya
SupervisorsDr. Ghufran Redzwan, Institute Of Biological Science, University of MalayaProf. Mohd. Ali Hashim, Department Of Chemical Engg.,University of MalayaProf. Bhaskar Sen Gupta, Heriot-Watt University, UK (External advisor)
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Presentation overview Introduction Problem statement Aim and Objectives Methodology Results and discussion Conclusion Future work
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INTRODUCTION
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• Industrialization, • Economic
growth, • Indiscriminate
use of resource, • No or poor
treatment method
• Heavy metals, • dyes, • Phenols, • Cyanides, • Acids, • Sulphates, • Organic
substances
• Highly toxic• Carcinogeni
c• Bio-
magnifying capacity
• Chemical precipitation,
• Ion-exchange, • Electrochemical
methods, • Membrane
filtration, • Coagulation–
flocculation, • Flotation, • Fenton method, • Photo-chemical
method and • Adsorption
Why adsorption?• Most
versatile,• Economic • Easy to use
technology
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Challenges in implementation of adsorption on activated carbon for wastewater treatment
Challenges during preparation
Reduction of
preparation time
Reduction of preparation
costRaw
material
Challenges during application
Space Time
Reduction in efficiency and increase in the operating cost
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Microwave technology
High gravimetric technology in rotating packed bed
(HIGEE-RPB)
Locally available agricultural
waste
AIMEnhancement of the efficiency and cost-effectiveness of adsorption process on activated carbon using advanced technologies.
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OBJECTIVE
1. Optimisation of process variables in microwave assisted activated carbon production from locally available waste material.
2. Evaluation of the efficacy of the prepared activated carbon for removal of heavy metal and dye.
3. Application of HIGEE technology in rotating packed bed contactor to minimise the contact time for adsorption.
4. Optimisation of the process parameters of rotating packed bed contactor for heavy metal and dye removal, estimation of the adsorption kinetics, adsorption isotherm.
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METHODOLOGY
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Preparation of activated carbon
from low cost agricultural
waste.
Optimization of preparation
conditions for microwave activation.
Characterisation of the
prepared activated carbon
Optimization of the adsorption process in RPB.
Designing and construction of rotating packed
bed reactor.
Adsorption test with the activated
carbon in RPB
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Name asserted to the prepared activated carbon
Microwave power (W)
Time of irradiation (min)
Ratio of Amount of precursor to Amount of 85% H3PO4
MWAC 1 900 20 1:1
MWAC 2 900 20 1:2
MWAC 3 900 20 1:3
Preparation condition
General approach : at varying impregnation ratio
Nitrogen gas flow rate wads 0.2 (l/min)
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Investigating parameters
Level 1 Level 2 Level 3 Level 4
Microwave Power (W) 400 600 800 1000
Time (min) 3 10 17 24
Impregnation ratio
(acid:pks)0.5 1 1.5 2
Conc. of acid (H3PO4) (%) 42.5 85
Levels of the control factors used as preparation parameters.
Experiment No
Microwave Power (W)
Time (min)
Impregnation ratio (acid:pks)
Conc. of acid
(H3PO4) (%)
1 400 3 0.5 42.52 400 10 1 42.53 400 17 1.5 854 400 24 2 855 600 3 1 856 600 10 0.5 857 600 17 2 42.58 600 24 1.5 42.59 800 3 1.5 85
10 800 10 2 8511 800 17 0.5 42.512 800 24 1 42.513 1000 3 2 42.514 1000 10 1.5 42.515 1000 17 1 8516 1000 24 0.5 85
Taguchi Optimization Approach (developed by Genichi Taguchi to improve the quality of manufactured goods)
L16 array for the different combination of experimental conditions
Advantages of Taguchi method
• Unique set of “orthogonal array” experiments, balanced with respect to all control factors
• Minimum in number. • Minimum use of resources and brings down the production
cost. • Large number of variables can be studied with a small
number of experiments.• Considers the effects of Noise factors which are inconvenient
to control • Make the process insensitive to the variables.
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L9 array for fine-tuning the experimental conditions
Investigating
parameters
Level
1
Level
2
Level
3
Microwave
Power (W)700 800 900
Irradiation
Time (min)13 17 21
Impregnation
ratio (acid :
PKS)
1 2 3
Impregnati
on ratio
Microwave
PowerTime
1 700 13
1 800 17
1 900 21
2 700 17
2 800 21
2 900 13
3 700 21
3 800 13
3 900 17
Levels of the control factors used in fine-tuning
experiment.
Signal to noise (S/N) ratio: larger-the-better= -10 log [mean of sum of square of reciprocal of measured data]Or = – 10 Log10 ( 1/n 1/Yi
2 )
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Response Surface Methodology (RSM) Optimization Approach
Factor
Name
Units
Type Low Actual
High Actual
Low Coded
High Coded
Mean
A Time min Numeric
5 20 -1 1 12.5
B Power W Numeric
600 1000 -1 1 800
C IR Numeric
0.5 2 -1 1 1.25
D Conc. of acid
% Numeric
20 100 -1 1 60
Summary of experimental design of preparation of activated carbon
Factor 1 Factor 2 Factor 3 Factor 4Run Type A:Time B:Power C:IR D:conc of acid
min W %1 Fact 20 1000 0.5 202 Fact 20 600 2 203 Center 12.5 800 1.25 604 Axial 12.5 800 0.5 605 Axial 12.5 800 2 606 Fact 5 600 0.5 207 Fact 5 600 0.5 1008 Fact 20 600 0.5 1009 Fact 20 1000 2 100
10 Axial 12.5 800 1.25 10011 Axial 5 800 1.25 6012 Fact 20 1000 2 2013 Axial 12.5 1000 1.25 6014 Fact 5 1000 2 2015 Fact 5 1000 0.5 10016 Center 12.5 800 1.25 6017 Fact 5 600 2 2018 Center 12.5 800 1.25 6019 Axial 12.5 600 1.25 6020 Axial 20 800 1.25 6021 Axial 12.5 800 1.25 2022 Center 12.5 800 1.25 6023 Fact 20 600 2 10024 Fact 20 600 0.5 2025 Fact 5 1000 0.5 2026 Fact 5 1000 2 10027 Fact 5 600 2 10028 Fact 20 1000 0.5 100
Advantages of CCD method
• CCD are very efficient, providing much information on experiment variable effects and overall experimental error in a minimum number of required runs.
• CCDs are very flexible. The availability of several varieties of CCDs enables their use under different experimental regions of interest and operability.
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RESULTS AND DISCUSSION
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PREPARATION OF ACTIVATED CARBON
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SampleAdsorbent pH
BET surface
area(m2 g-1)
Total pore volume(cc g-1)
Average Pore
Diameter(Å)
MWAC 1 5.92 872 0.598 27.4MWAC 2 6 1256 1.010 32.4MWAC 3 6 952 0.778 32.7MWAC T 5 1535 1.022 27.8
MWAC CCD 4.9 1011 0.553 21.89
Physico-chemical properties of the prepared activated carbons
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SEM micrographs and FTIR spectra of the raw material (A and C) and prepared activated carbon at optimized condition (B and D) depicting surface characteristics for MWAC T.
SEM micrographs and FTIR spectra of the raw material (A and C) and prepared activated carbon at optimized condition (B and D) depicting surface characteristics for MWAC CCD
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Effects of the Control Factors on S/N ratio for the AC Preparation by Taguchi Method
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The largest S/N performance corresponds to the best performance characteristic.
Optimum operating conditionsIrradiation Time (min)
Power (Watt)
Impreg-nation ratio
Acid con (%)
17 800 2 Undiluted (85 %) H3PO4
After fine-tune17 700 2 N/A
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Effect of Multiple Variables During the Preparation of AC by CCD Optimization Method
Three dimensional graphical representation of the interaction between (A) time and power, (B) time and IR, (C) power-IR, and (D) time and concentration of acid for Zn adsorption
Optimum operating conditionsIrradiation Time (min)
Power (Watt)
Impreg-nation ratio
Acid conc. (%)
11 676 0.68 Undiluted H2SO4
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APPLICATION OF THE ACTIVATED CARBON ANDEVALUATION OF HIGEE TECHNOLOGY IN ROTATING PACKED BED CONTACTOR
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Adsorption of Chromium on MWAC 2Design-Expert® Software
Adsorption19.075
4.495
X1 = A: Initial Conc.X2 = B: pH
Actual FactorC: Temp = 35.00
20.00
30.00
40.00
50.00
60.00
1.00
2.00
3.00
4.00
5.00
3
6.5
10
13.5
17
A
dsor
ptio
n
A: Initial Conc. B: pH
Design-Expert® Software
Adsorption19.075
4.495
X1 = A: Initial Conc.X2 = C: Temp
Actual FactorB: pH = 3.00
20.00
30.00
40.00
50.00
60.00
20.00
27.50
35.00
42.50
50.00
8
11
14
17
20
A
dsor
ptio
n
A: Initial Conc. C: Temp Design-Expert® Software
Adsorption19.075
4.495
X1 = B: pHX2 = C: Temp
Actual FactorA: Intical Conc. = 60.00
1.00
2.00
3.00
4.00
5.00
20.00
27.50
35.00
42.50
50.00
8
11
14
17
20
A
dsor
ptio
n
B: pH C: Temp
Design-Expert® Software
Adsorption19.075
4.495
X1 = A: Initial Conc.X2 = C: Temp
Actual FactorB: pH = 3.00
20.00
30.00
40.00
50.00
60.00
20.00
27.50
35.00
42.50
50.00
8
11
14
17
20
A
dsor
ptio
n
A: Initial Conc. C: Temp
Design-Expert® Software
Adsorption19.075
4.495
X1 = A: Initial Conc.X2 = B: pH
Actual FactorC: Temp = 35.00
20.00
30.00
40.00
50.00
60.00
1.00
2.00
3.00
4.00
5.00
3
6.5
10
13.5
17
A
dsor
ptio
n
A: Initial Conc. B: pH
Design-Expert® Software
Adsorption19.075
4.495
X1 = B: pHX2 = C: Temp
Actual FactorA: Intical Conc. = 60.00
1.00
2.00
3.00
4.00
5.00
20.00
27.50
35.00
42.50
50.00
8
11
14
17
20
A
dsor
ptio
n
B: pH C: Temp
(B)(A)
(C)
A) Combined effect of initial concentration and pH for chromium adsorption; B) combined effect of initial concentration and temperature; and C) combined effect of pH and temperature
Initial concentration(mg L-
1)
pH
Temp
(oC)
Suggested removal (mg gm-
1)
Obtained removal (mg gm-1)
60 3 50 18.25 19.1
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Temperature (K)
k1(min-1)
k2(g mg-1
min-1)R
2
298 0.0044 0.00220.8046 (first
order)0.9931(seco
nd order)
Kinetic Model Parameters
Isotherm Model ParametersLangmuir Isotherm
Freundlich Isotherm Temkin Isotherm Dubinin–
Radushkevichqmax (mg gm-1)
17.57469 Kf (L g-1) 5.199695 A (L g-1) 1.73 qm 15.63
b (L g-1) 0.203943 1/n 0.3047 b (kJ mol-1) 0.645 K x 10-6
(mol2 kJ-2) 2
n 3.282 E (kJ mol-1) 0.5
R2 0.9593 R2 0.9697 R2 0.8731 R2 0.7507
Pseudo second order kinetics rate limiting step in the adsorption is mainly chemisorption which involves valency forces resulted in due to sharing or exchange of electrons between adsorbent and adsorbate
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• The centrifugal force generated in the rotating packed bed, influenced the removal of the dye with the aid of increasing mass transfer coefficient.
• The adsorption was fast and within 5 hours, almost 93% dye removal was obtained compared to 54% in traditional shake flask experiment.
• Rotating speed of the rotor and liquid feed rate had significant effect on the removal of the dye.
0 50 100 150 200 250 300 3500102030405060708090
100Comparison dye removal in RPB and Shake flask
% Re-moval RPB 50% Re-moval RPB 100% Re-moval SF 50% Re-moval SF 100
Time, minutes
Perc
ent
rem
oval
Removal of Direct Red 23 in RPB
0 20 40 60 80 100 120 1400
20
40
60
80
100
Effect of rotor speed on adsorption of direct red 23. 628 rpm
855 rpm
1140 rpm
Time, minutes
Perc
ent r
emov
al
0 20 40 60 80 100 120 1400
20
40
60
80
100Effect of feed rate on adsorption of direct red
23.10 L/h
20 L/h
30 L/h
40 L/h
Time, minutes
Perc
ent r
emov
al
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Experiments
Initial
concentrati
on (mg/L
)
qe, exp
(mg/g)
Pseudo-first-order kinetic
model
Pseudo-second-order kinetic model
Intra-particle diffusion
qe,
cal
k1 R2 qe, cal k2 R2 kipd R2
Rotating
packed bed
50 10.1210.1
0.012
0.9617
11.590.008
0.9431 0.604 0.9903
100 14.7316.63
0.008
0.9412
24.940.003
0.4866 0.896 0.9435
Shake flask
50 5.475.34
0.010
0.9738
6.320.027
0.9125 0.324 0.9878
100 8.458.97
0.009
0.9728
11.170.011
0.757 0.517 0.9749
Pseudo-first order, Pseudo-second-order and intra-particle diffusion parameter values
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Levels of the control factors used.
Chromium Removal in RPB L16 array for the different combination of experimental conditions
Investigating parameters
Level 1 Level 2 Level 3 Level 4
Rotating speed (rpm)
400 800 1200 1600
Feed rate (L/h) 20 30 40 50Packing density (kg/m3)
153 255 357 510
Initial Solution pH 2 3 4 5
Rotating
speedFeed rate
Packing density
Initial pH
Percent removal of Cr(VI)
NF 1 NF 2 NF 3
400 20 153 2 60.18 59.57 58.1400 30 255 3 64.5 63.46 63.45400 40 357 4 55.3 55.09 55.02400 50 510 5 50.47 59.78 59.65800 20 255 5 63.1 62.43 61.1800 30 153 4 60.93 68.44 62.25800 40 510 3 81.77 84.87 84.43800 50 357 2 85.69 84.23 84.191200 20 357 3 66.1 65.72 65.711200 30 510 2 77.03 75.67 75.431200 40 153 5 92.46 87.79 92.131200 50 255 4 80.92 80.8 82.771600 20 510 4 67.88 68.04 68.851600 30 357 5 87.53 86.9 86.821600 40 255 2 67.48 65.49 63.231600 50 153 3 73.28 72.56 72.78
Taguchi optimisation approach was used.
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Investigating parameters
Level Value Predicted Experimental
Rotating speed (rpm)
3 1200 S/N ratio
Mean S/N ratio
Mean
Feed rate (L/h)
4 50 39.20
90.34
39.26
91.83
Packing
density (kg/m3)
3 357
Initial Solution pH
1 2
Effect of the Control Factors
Optimum operating conditions
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0 100 200 300 400 500 600 7000
10
20
30
40
50
60
70
80
90
100
Time (min)
% re
mov
al
Removal of chromium with respect to time in RPB
• About 75% was removed within 20 min
• About 90% removal with in 3 h• Based on the R2 value the second
order kinetics (0.9989) can describe the adsorption kinetics hence chemisorption.
Kinetics of Adsorption in RPB
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• This research was conceived with the objective of advancement of adsorption on activated carbon in wastewater treatment.
• Microwave and high gravimetric technologies were used to reduce the time
and energy use of the total process.
• With the aid of microwave technology the production time of activated carbon was considerably short (17 min and 11 min) hence requiring less energy than conventional process.
Conclusion
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• High gravimetric technology in RPB was employed to reduce the equipment size and faster removal of heavy metal and dye from wastewater. In RPB heavy metal and dye from water were removed successfully. Removal was fast and effectively.
• Thus this study describes an effective production method to produce highly surface area activated carbon from less valuable agricultural carbonaceous biomass. Combination of a advanced microwave technology for heating and high gravimetric technology for intensification of the adsorption process, with optimized processing variables has reduced time and energy usage for the removal of heavy metal and dye from wastewater thus making the process more economic, environment friendly and sustainable.
Conclusion (cont..)
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FUTURE WORK The scaling up of the microwave system to produce substantial
quantity of the activated carbon must be considered to match up with the requirement of the industry.
Other heavy metals as well as dyes must also be tested for adsorption on to activated carbon in RPB.
A detail experiments on regeneration of the spent activated carbon are also required to be examined to make the system even more sustainable and environment friendly.
Scale up of the RPB system is also to be considered for industrial use.
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List of Publications
1. Kundu, A., SenGupta, B., & Hashim, M. A., Redzwan, G. (2015) Taguchi optimization approach for production of activated carbon from phosphoric acid impregnated palm kernel shell by microwave heating. Journal of Cleaner Production, 105, 420-427. (ISI Q1, IF: 3.844)
2. Kundu, A., Hashim, M. A., SenGupta, B., Sahu, J. N., Mubarak, N. M., & Redzwan, G. (2015). Optimization of the process variables in production of activated carbon by microwave heating. RSC Advances, 5, 35899-35908. (ISI Q1, IF: 3.840)
3. Kundu, A., SenGupta, B., Hashim, M. A., Redzwan, G. (2015) Taguchi optimisation approach for chromium removal in a rotating packed bed contractor. Journal of the Taiwan Institute of Chemical Engineers, 57, 91-97. (ISI Q1, IF: 3.000)
4. Kundu, A., Hassan L. S., Redzwan, G., Robinson, D., Hashim, M. A., SenGupta, B. (2015). Application of a rotating packed bed contactor for removal of Direct Red 23 by adsorption. Desalination and Water Treatment (Accepted) (ISI Q3, IF: 1.173)
5. Kundu, A., Redzwan, G., Sahu, J. N., Mukherjee, S., SenGupta, B., & Hashim, M. A. (2014). Hexavalent Chromium Adsorption by a Novel Activated Carbon Prepared by Microwave Activation. BioResources, 9(1), 1498-1518. (ISI Q1 IF: 1.309)
6. Mubarak, N. M., Kundu, A., Sahu, J. N., Abdullah, E. C., & Jayakumar, N. S. (2014). Synthesis of palm oil empty fruit bunch magnetic pyrolytic char impregnating with FeCl3 by microwave heating technique. Biomass and Bioenergy, 61, 265–275. (ISI Q1, IF: 3.394)
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THANK YOU
University of Malaya (Project no. UM.C/HIR/MOHE/ENG/13 And IPPP project no. Pg040-2012b) for providing the funds for the research work.